General synthetic strategy for fabrication of multi-metallic nanostructures

ABSTRACT

A method for preparing a hollow multi-metallic nanostructure, the method including the steps of providing a first metal nanostructure having a plurality of first metal atoms, and performing a synthetic strategy, the synthetic strategy including replacing a portion of the plurality of first metal atoms with a corresponding number of second metal ions, and promoting first metal atom diffusion to provide the hollow multi-metallic nanostructure.

TECHNICAL FIELD

The present disclosure is directed to a method for producing hollowmulti-metallic nanostructures.

BACKGROUND OF THE DISCLOSURE

Multi-metallic hollow nanostructures are promising new candidates inbiomedicine, fuel cells, and gas sensors due to their porous structuresand possible synergistic effects between the two or more metals.However, known methods for synthesizing such nanostructures generallyinvolve individualized synthetic methods. Although a few general methodsare known, such methods are generally limited to noble metals, such assilver or palladium, both of which are expensive when compared withother metals, such as copper. There is thus a need in the art for ageneral synthetic strategy for preparing multi-metallic nanostructures.

BRIEF DESCRIPTION OF THE DISCLOSURE

The present disclosure is directed generally to a method for preparinghollow multi-metallic two-dimensional nanostructures. The method maycomprise providing a first metal nanostructure, replacing a portion ofthe first metal atoms comprised by the first metal nanostructure with acorresponding number of second metal ions, and promoting first metalatom diffusion to provide a hollow nanostructure. According to someaspects, the method may comprise a one-step synthetic strategy. Thepresent disclosure is also directed to hollow multi-metallictwo-dimensional nanostructures provided by the present method.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the Office upon request and paymentof the necessary fee.

FIG. 1 shows an example schematic of the method according to aspects ofthe present disclosure.

FIG. 2 shows a scanning electron microscopy (SEM) image of the hollowAu—Cu two-dimensional nanostructure prepared according to Example II(a).

FIG. 3 shows a transmission electron microscopy (TEM) image of thehollow Au—Cu two-dimensional nanostructure prepared according to ExampleII(a).

FIG. 4 shows a high-resolution TEM (HRTEM) image of the hollow Au—Cutwo-dimensional nanostructure prepared according to Example II(a).

FIG. 5 shows the high-angle annular dark-field scanning transmissionelectron microscopy (HAADF-STEM) image of the hollow Au—Cutwo-dimensional nanostructure prepared according to Example II(a).

FIG. 6 shows an energy dispersive X-ray (EDX) mapping image of the Cuelement of the hollow Au—Cu two-dimensional nanostructure preparedaccording to Example II(a).

FIG. 7 shows an energy dispersive X-ray (EDX) mapping image of the Auelement of the hollow Au—Cu two-dimensional nanostructure preparedaccording to Example II(a).

FIG. 8 shows the Cu—Au alloying evolution process of Example II(a) overtime.

FIG. 9A shows a X-ray photoelectron spectroscopy (XPS) spectrum of theAu element of the hollow Au—Cu two-dimensional nanostructure preparedaccording to Example II(a).

FIG. 9B shows a X-ray photoelectron spectroscopy (XPS) spectrum of theCu element of the hollow Au—Cu two-dimensional nanostructure preparedaccording to Example II(a).

FIG. 10 shows a scattering spectrum of the hollow Au—Cu two-dimensionalnanostructure prepared according to Example II(a).

FIG. 11A shows SEM and TEM images of the Cu—Pd hollow nanostructuresprepared according to Examples II(b).

FIG. 11B shows SEM and TEM images of the Cu—Pt hollow nanostructuresprepared according to Examples II(c).

FIG. 11C shows SEM and TEM images of the Cu—Au hollow nanotubes preparedaccording to Examples II(d).

DETAILED DESCRIPTION OF THE DISCLOSURE

The present disclosure is directed generally to a method for preparinghollow multi-metallic nanostructures. The method may comprise providinga first metal nanostructure, replacing a portion of the first metalatoms comprised by the first metal nanostructure with a correspondingnumber of second metal ions, and promoting first metal atom diffusion toprovide a hollow nanostructure. According to some aspects, the methodmay comprise a one-step synthetic strategy. The present disclosure isalso directed to hollow multi-metallic nanostructures provided by thepresent method. Optionally, the nanostructures may be two dimensional.

As used herein, the term “nanostructure” refers to a structure having atleast one dimension on the nanoscale, that is, at least on dimensionbetween about 0.1 and 100 nm. It should be understood that“nanostructures” include, but are not limited to, nanosheets, nanotubes,nanoparticles (e.g., polyhedral nanoparticles), nanospheres, nanowires,nanocubes, and combinations thereof. A nanosheet may comprise a sheethaving a thickness on the nanoscale. A nanotube may comprise a tubehaving a diameter on the nanoscale. A nanoparticle may comprise aparticle wherein each spatial dimension thereof is on the nanoscale.According to some aspects, the first metal nanostructure and the hollowmulti-metallic two-dimensional nanostructures may be the same ordifferent.

According to some aspects, the method may comprise providing a firstmetal nanostructure, such as a first metal nanosheet. It should beunderstood that the first metal nanostructure may be provided by anymeans known in the art compatible with the present disclosure.

For example, according to some aspects, the first metal nanostructuremay comprise a copper nanosheet. According to some aspects, the coppernanosheet may be provided using a copper complex solution. According tosome aspects, the copper complex solution may comprise one or morecopper complexes. As used herein, the term “copper complex” refers to acomplex of copper and one or more complexing agents. Complexing agentsuseful according to the present disclosure include, but are not limitedto, tetradecylamine (TDA), dodecylamine (DDA), hexadecylamine (HAD),octadecylamine (ODA), and oleylamine (OLA). According to some aspects,the copper complex may be provided by combining one or more copper atomsand/or salts thereof with one or more complexing agents in a solutionunder an inert atmosphere and stirring for an acceptable length of timeat an acceptable temperature. For example, the copper complex may beprovided by combining a copper salt and one or more complexing agents ina solution under an inert gas flow. Examples of inert gases include, butare not limited to, nitrogen gas, argon gas, and combinations thereof.The combined solution may then be heated to a temperature of betweenabout 100 and 300° C. from about one minute to about one hour to providea copper complex solution comprising the copper complex.

According to some aspects, the copper nanosheet may be provided byheating the copper complex solution. For example, the copper nanosheetmay be provided by combining the copper complex solution with one ormore ligands at an elevated temperature under an inert atmosphere for anacceptable length of time. For example, the copper nanosheet may beprovided by combining the copper complex solution with a ligand under aninert atmosphere at an elevated temperature of between about 100 and500° C., optionally between about 200 and 400° C., and optionally about300° C. The combined solution may be held at the elevated temperaturefor a time of between about one minute and two hours, optionally betweenabout thirty and ninety minutes, and optionally about one hour, toprovide a copper nanosheet solution containing the copper nanosheets.Examples of ligands include, but are not limited to, oleylamine,trioctylphosphine, tetradecylamine, dodecylamine, octadecylamine,hexadecylamine, trioctylphosphine oxide, oleic acid, and combinationsthereof.

It should be understood that the first metal atoms comprised by thefirst metal nanostructure (for example, copper atoms comprised by coppernanosheets) will have a first oxidation potential. As used herein, theterm “oxidation potential” refers to the energy change required toremove electrons from a material. It should be understood that copper,for example, may have an oxidation potential of about 0.34 V. Accordingto some aspects, the first metal may be a metal with a first oxidationpotential of no more than about 1.0 V, optionally no more than about 0.5V. According to some aspects, the first metal may be selected from thegroup consisting of copper (Cu), nickel (Ni), cobalt (Co), iron (Fe),and combinations thereof.

According to some aspects, the method may comprise replacing a portionof the first metal atoms comprised by the first metal nanostructure witha corresponding number of second metal ions. According to some aspects,the second metal may comprise a metal having a second oxidationpotential, wherein the second oxidation potential is greater than thefirst oxidation potential. Examples of metals useful according to thepresent disclosure include, but are not limited to, gold (Au), platinum(Pt), palladium (Pd), and combinations thereof. According to someaspects, the second oxidation potential may be about 1.40 V (Au³⁺/Au),about 1.20 V (Pt²⁺/Pt), and/or about 0.92 V (Pd²⁺/Pd). According to someaspects, the second oxidation potential may be at least about 0.6 Vgreater than the first oxidation potential, optionally about 0.7 Vgreater, optionally about 0.8 V greater, optionally about 0.9 V greater,and optionally about 1.0 V greater. According to some aspects, the firstmetal is different from the second metal.

According to some aspects, replacing a portion of the first metal atomscomprised by the first metal nanostructure with a corresponding numberof second metal ions may comprise combining a first metal nanostructuresolution with a metal precursor solution. As used herein, the term“first metal nanostructure solution” refers to a solution comprising thefirst metal nanostructure as described herein. As used herein, the term“metal precursor solution” refers to a solution comprising ametal-containing compound and/or hydrates thereof. Examples of metalcompounds include, but are not limited to, chloroauric acid (HAuCl₄),palladium(II) acetylacetonate (Pd(acac)₂), chloroplatinic acid(H₂PtCl₆), combinations thereof, and hydrates thereof. According to someaspects, the first metal nanostructure solution may be combined with themetal precursor solution at a temperature suitable for the second metalions to replace a corresponding number of first metal ions. For example,the first metal nanostructure solution may be combined with the metalprecursor solution at an elevated temperature of between about 10 and200° C., optionally between about 50 and 180° C., optionally betweenabout 80 and 180° C., and optionally between about 80 and 150° C.

According to some aspects, the concentration and/or amount of the firstmetal nanostructure solution and/or the metal precursor solution may beselected in order to provide a combined solution having at least aninitial molar ratio of first metal atoms to second metal ions from about5:1 to about 1:5, optionally from about 4:1 to 1:4, and optionally fromabout 3:1 to 1:3.

According to some aspects, the molar ratio of first metal atoms tosecond metal ions may be selected in order to provide a selectedcomposition and phase of the resulting hollow multi-metallictwo-dimensional nanostructure. In particular, according to some aspects,the reaction rate of galvanic replacement may increase with an increasedconcentration of metal precursor. As such, the reaction rate of galvanicreplacement may be selected by selecting a certain molar ratio of firstmetal atoms to second metal ions in the combined solution.

The combined first metal nanostructure and metal precursor solution maybe held at the elevated temperature for a synthesis time of betweenabout 1 minute and 3 hours, optionally between about 20 minutes and 2hours, and optionally about 1 hour, such that a portion of the firstmetal atoms comprised by the first metal nanostructure is replaced witha corresponding number of second metal ions. According to some aspects,the synthesis time may be selected in order to provide a selectedcomposition and phase of the resulting hollow multi-metallictwo-dimensional nanostructure. For example, a longer synthesis time(e.g., 20 minutes) may result in a hollow multi-metallic two-dimensionalnanostructure having a molar ratio of first metal atoms to second metalatoms of about 1:1, whereas a shorter synthesis time (e.g., less than 5minutes) may result in a hollow multi-metallic two-dimensionalnanostructure having a molar ratio of first metal atoms to second metalatoms of about 3:1. Because the concentration of first metal atomscomprised by the nanostructure may decrease with an increased reactiontime, when the reaction time prolongs to 40 minutes, the molar ratio offirst metal to second metal atoms may reduce to 1:3. The final molarratio of first metal to second metal atoms may reach 1:8 with a reactiontime of 60 minutes.

According to some aspects, the portion of replaced first metal ions maycomprise first metal ions located at or near the surface of the firstmetal nanostructure. Without wishing to be bound by a particular theory,because the first oxidation potential is less than the second oxidationpotential, first metal atoms at or near a nanostructure's surface may bereplaced with second metal ions due to galvanic replacement.

According to some aspects, the method may comprise promoting first metalatom diffusion to provide hollow multi-metallic two-dimensionalnanostructures. Without wishing to be bound by a particular theory, thehollow multi-metallic two-dimensional nanostructures may be provided bythe Kirkendall effect, wherein first metal atoms interior to the firstmetal nanostructure diffuse to the exterior of the nanostructure. Asused herein, the term “exterior” refers to a position at and/or near thesurface of the nanostructure. The term “interior” refers to a positionaway from the surface of the nanostructure. It should be understood thatthe hollow multi-metallic two-dimensional nanostructures may comprise,for example, a continuous hollow center (i.e., wherein the hollow centerspans from one side of the nanostructure to another to form, e.g., aring- or tube-shaped nanostructure) and/or may comprise a hollow core(i.e., wherein the hollow center does not span from one side of thenanostructure to another, and instead forms an indent-shaped center inthe nanostructure or a hollow center that is not visible from theoutside of the nanostructure).

According to some aspects, one or more of the other method steps asdescribed herein may sequentially and/or simultaneously promote firstmetal atom diffusion. For example, combining the first metalnanostructure solution and the metal precursor solution at an elevatedtemperature suitable for the second metal ions to replace acorresponding number of first metal ions and holding the combinedsolution at the elevated temperature, as described herein, maysequentially and/or simultaneously replace a portion of the first metalatoms comprised by the first metal nanostructure with a correspondingnumber of second metal ions and promote first metal atom diffusion.

According to some aspects, the method may comprise a one-step syntheticstrategy. As used herein, the term “one-step synthetic strategy” refersto a synthetic strategy wherein at least a first reactant is convertedto a reaction product in a single synthesis step. For example, asdescribed herein, the first metal nanostructure may be converted to thehollow multi-metallic two-dimensional nanostructure in a singlesynthesis step, in particular, combining the first metal nanostructuresolution and the metal precursor solution at the elevated temperatureand holding the combined solution at the elevated temperature for acertain length of time.

FIG. 1 shows an example schematic of the method according to aspects ofthe present disclosure. As shown in FIG. 1, the method may compriseproviding one or more first metal nanostructures, for example, one ormore copper nanosheets 11. The method may comprise replacing a portionof the copper atoms 12 comprised by the copper nanosheet with acorresponding number of second metal ions, such as Au ions 13, Pd ions14, and/or Pt ions 15. As described herein, replacing a portion of thecopper atoms 12 comprised by the copper nanosheet with a correspondingnumber of second metal ions may comprise combining a solution containingthe one or more copper nanosheets 11 with a metal precursor solution atan elevated temperature for a certain period of time. As describedherein, carbon atoms may sequentially and/or simultaneously diffuse toprovide the hollow multi-metallic two-dimensional nanostructures 16 asdescribed herein.

According to some aspects, the method may further comprise one or morewashing steps. The washing step may comprise centrifuging the solutioncontaining the hollow multi-metallic two-dimensional nanostructures,removing the supernatant, combining with a solvent such as a hydrophobicsolvent and/or an organic solvent, and centrifuging the combinedsolution. The method may comprise one, two, three, or more washingsteps.

It should be understood that the term “multi-metallic” as used hereinrefers to at least two different metals. According to some aspects, thehollow multi-metallic two-dimensional nanostructure may be a hollowbimetallic two-dimensional nanostructure, that is, wherein the onlymetal atoms comprised by the nanostructure are the first and secondmetal atoms. However, according to some aspects, the hollowmulti-metallic two-dimensional nanostructure may comprise three, four,five, or more different kinds of metal atoms.

The present disclosure is also directed to hollow multi-metallictwo-dimensional nanostructures provided by the present method,including, but not limited to, Cu—Au hollow nanostructures, Cu—Pd hollownanostructures, Cu—Pt hollow nanostructures. According to some aspects,the molar ratio of the first metal to the second metal atoms in thehollow multi-metallic two-dimensional nanostructure may be from about10:1 to 1:10, optionally from about 5:1 to 1:5, optionally from about3:1 to 1:3, optionally from about 2:1 to 1:2, optionally from about1.5:1 to 1:1.5, and optionally about 1:1.

The present disclosure is also directed to methods of using the hollowmulti-metallic two-dimensional nanostructures as described herein.According to some aspects, the method may comprise utilizing the hollowmulti-metallic two-dimensional nanostructures in the production of gassensors and/or use of the resulting gas sensors. According to someaspects, the method may comprise using the hollow multi-metallictwo-dimensional nanostructures to, at least in part, catalyze CO₂reduction reactions.

While the aspects described herein have been described in conjunctionwith the example aspects outlined above, various alternatives,modifications, variations, improvements, and/or substantial equivalents,whether known or that are or may be presently unforeseen, may becomeapparent to those having at least ordinary skill in the art.Accordingly, the example aspects, as set forth above, are intended to beillustrative, not limiting. Various changes may be made withoutdeparting from the spirit and scope of the disclosure. Therefore, thedisclosure is intended to embrace all known or later-developedalternatives, modifications, variations, improvements, and/orsubstantial equivalents.

Thus, the claims are not intended to be limited to the aspects shownherein, but are to be accorded the full scope consistent with thelanguage of the claims, wherein reference to an element in the singularis not intended to mean “one and only one” unless specifically sostated, but rather “one or more.” All structural and functionalequivalents to the elements of the various aspects described throughoutthis disclosure that are known or later come to be known to those ofordinary skill in the art are expressly incorporated herein by referenceand are intended to be encompassed by the claims. Moreover, nothingdisclosed herein is intended to be dedicated to the public regardless ofwhether such disclosure is explicitly recited in the claims. No claimelement is to be construed as a means plus function unless the elementis expressly recited using the phrase “means for.”

Further, the word “example” is used herein to mean “serving as anexample, instance, or illustration.” Any aspect described herein as“example” is not necessarily to be construed as preferred oradvantageous over other aspects. Unless specifically stated otherwise,the term “some” refers to one or more. Combinations such as “at leastone of A, B, or C,” “at least one of A, B, and C,” and “A, B, C, or anycombination thereof” include any combination of A, B, and/or C, and mayinclude multiples of A, multiples of B, or multiples of C. Specifically,combinations such as “at least one of A, B, or C,” “at least one of A,B, and C,” and “A, B, C, or any combination thereof” may be A only, Bonly, C only, A and B, A and C, B and C, or A and B and C, where anysuch combinations may contain one or more member or members of A, B, orC. Nothing disclosed herein is intended to be dedicated to the publicregardless of whether such disclosure is explicitly recited in theclaims.

As used herein, the term “about” and “approximately” are defined tobeing close to as understood by one of ordinary skill in the art. In onenon-limiting embodiment, the term “about” and “approximately” aredefined to be within 10%, preferably within 5%, more preferably within1%, and most preferably within 0.5%.

EXAMPLES Example I: Preparation of Copper Complex Solution

100 mg of copper (I) chloride (99.99%). 220 mg of tetradecylamine(TDA.>96%), and 2 mL of ODE were added into a flask where oxygen wasremoved under Ar or N₂ flow. After Ar or N₂ blowing for 20 minutes, themixed solution was heated to 190° C. on a hot plate and kept at thistemperature for 30 minutes. During the heating process, TDA was meltedat about 38 to 40° C. and coordinated with Cu atoms to form a Cu-TDAblue complex solution.

Example II(a): Synthesis of Cu—Au Hollow Nanostructures

6.0 mL of OLA (70%) was loaded into a 25 mL three-neck flask whereoxygen was removed through Ar blowing for 10 minutes. Under Ar flow, 0.5mL of TOP (97%) and 0.5 mL of TOP (90%) were injected into the flask,respectively. After 10 minutes of Ar flowing, the flask was rapidlyheated to 300° C. Next, 2 mL of the copper complex solution prepared inExample I was quickly injected into the hot flask and the reactionsolution turned to red within 5-10 minutes, which indicated that coppernanosheets had formed. The reaction was held at 300° C. for 60 minutes.The reaction mixture was then naturally cooled to 120° C., and 1.0 mL ofgold precursor solution (0.1 M, 39.3 mg of HAuCl₄.3H₂O dissolved in 1.0mL of oleylamine) was injected. The reaction solution was kept at 120°C. for 60 minutes. The products were separated by centrifuging at 8000rpm for 5 minutes. The supernatant was discarded. A mixed solution of 5mL of hexane (or another hydrophobic solvent such as toluene orchloroform) and 5 mL of ethanol was then added to the sediment, and themixture was centrifuged at 8000 rpm for 5 minutes. The washing procedurewas repeated twice to remove unreacted precursors and surfactant. TheCu—Au hollow nanostructures were stored in hydrophobic solvents (e.g.,hexane, toluene, and chloroform) before characterization.

It was concluded that the injected gold precursor solution may be from0.2 mL to 3.0 mL, the injection temperature of gold precursor solutionmay be from 80° C. to 150° C., and the reaction time after injecting thegold precursor solution may be from 20 to 120 minutes to provideacceptable results.

Example II(b): Synthesis of Cu—Pd Hollow Nanostructures

6.0 mL of OLA (70%) was loaded into a 25 mL three-neck flask whereoxygen was removed through Ar blowing for 10 minutes. Under Ar flow, 0.5mL of TOP (97%) and 0.5 mL of TOP (90%) were injected into the flask,respectively. After 10 minutes of Ar flowing, the flask was rapidlyheated to 300° C. Next, 2 mL of the copper complex solution prepared inExample I was quickly injected into the hot flask and the reactionsolution turned to red within 5-10 minutes, which indicated that coppernanosheets had formed. The reaction was held at 300° C. for 60 minutes.The reaction mixture was then naturally cooled to 150° C. and 1.0 mL ofgold precursor solution (0.1 M, 30.4 mg of Pd(acac)₂ dissolved in 1.0 mLof oleylamine) was injected. The reaction solution was kept at 150° C.for 60 minutes. The products were separated by centrifuging at 8000 rpmfor 5 minutes. The supernatant was discarded. A mixed solution of 5 mLof hexane (or another hydrophobic solvent such as toluene or chloroform)and 5 mL of ethanol was then added to the sediment, and the mixture wascentrifuged at 8000 rpm for 5 minutes. The washing procedure wasrepeated twice to remove unreacted precursors and surfactant. The Cu—Pdhollow nanostructures were stored in hydrophobic solvents (e.g., hexane,toluene and chloroform) before characterization.

It was concluded that the injected palladium precursor solution may befrom 0.2 mL to 3.0 mL, the injection temperature of palladium precursorsolution may be from 80° C. to 180° C., and the reaction time afterinjecting the gold precursor solution may be from 20 to 120 minutes toprovide acceptable results.

Example II(c): Synthesis of Cu—Pt Hollow Nanostructures

6.0 mL of OLA (70%) was loaded into a 25 mL three-neck flask whereoxygen was removed through Ar blowing for 10 minutes. Under Ar flow, 0.5mL of TOP (97%) and 0.5 mL of TOP (90%) were injected into the flask,respectively. After 10 minutes of Ar flowing, the flask was rapidlyheated to 300° C. Next, 2 mL of the copper complex solution prepared inExample I was quickly injected into the hot flask and the reactionsolution turned to red within 5-10 minutes, which indicated that coppernanosheets had formed. The reaction was held at 300° C. for 60 minutes.The reaction mixture was then naturally cooled to 120° C. and 1.0 mL ofplatinum precursor solution (0.1 M, 51.7 mg of H₂PtCl₆·6H₂O dissolved in1.0 mL of oleylamine) was injected. The reaction solution was kept at120° C. for 60 minutes. The products were separated by centrifuging at8000 rpm for 5 minutes. The supernatant was discarded. A mixed solutionof 5 mL of hexane (or another hydrophobic solvent such as toluene orchloroform) and 5 mL of ethanol was then added to the sediment, and themixture was centrifuged at 8000 rpm for 5 minutes. The washing procedurewas repeated twice to remove unreacted precursors and surfactant. TheCu—Pt hollow nanostructures were stored in hydrophobic solvents (e.g.,hexane, toluene and chloroform) before characterization.

It was concluded that the injected platinum precursor solution may befrom 0.2 mL to 3.0 mL, the injection temperature of platinum precursorsolution may be from 80° C. to 150° C., and the reaction time afterinjecting the platinum precursor solution may be from 20 to 120 minutesto provide acceptable results.

Example II(d): Synthesis of Cu—Au Hollow Nanostructures

6.0 mL of OLA (70%) was loaded into a 25 mL three-neck flask whereoxygen was removed through Ar blowing for 10 minutes. Under Ar flow, 0.2mL of TOP (97%) was injected into the flask. After 10 minutes of Arflowing, the flask was rapidly heated to 300° C. Next, 2 mL of thecopper complex solution prepared in Example I was quickly injected intothe hot flask and the reaction solution turned to red within 5-10minutes, which indicated that copper nanosheets had formed. The reactionwas held at 300° C. for 20 minutes. The reaction mixture was thennaturally cooled to 120° C. and 1.0 mL of gold precursor solution (0.1M, 50.7 mg of HAuCl₄·3H₂O dissolved in 1.0 mL of oleylamine) wasinjected. The reaction solution was kept at 120° C. for 60 minutes. Theproducts were separated by centrifuging at 8000 rpm for 5 min. Thesupernatant was discarded. A mixed solution of 5 mL of hexane (oranother hydrophobic solvent such as toluene or chloroform) and 5 mL ofethanol was then added to the sediment, and the mixture was centrifugedat 8000 rpm for 5 minutes. The washing procedure was repeated twice toremove unreacted precursors and surfactant. The Cu—Au hollownanostructures were stored in hydrophobic solvents (e.g., hexane,toluene and chloroform) before characterization.

It was concluded that the injected gold precursor solution may be from0.2 mL to 3.0 mL, the injection temperature of gold precursor solutionmay be from 80° C. to 150° C., and the reaction time after injecting thegold precursor solution may be from 20 to 120 minutes to provideacceptable results.

Example III: Characterization of Hollow Nanostructures

The surface morphologies of the hollow nanostructures obtained inExample II were investigated by a scanning electron microscope (SEM,QUANTA FEG 650) from FEI with a field emitter as the electron source.Transmission electron microscopy (TEM) images were captured using an FEITecnai 20 microscope with an accelerating voltage of 200 kV. EnergyDispersive X-Ray spectrometer (EDS) mapping image and the high-angleannular dark-field (HAADF) image were collected by employing theprobe-corrected Titan³™ 80-300 S/TEM with an accelerating voltage of 300kV. A UV-Vis-NIR spectrometer (Cary 5000) was used to record theextinction spectra of the hollow nanostructures. A Bruker D8 AdvanceX-ray diffractometer with Cu Kα radiation operated at a tube voltage of40 kV and a current of 40 mA was used to obtain X-ray diffraction (XRD)patterns. The surface composition of Cu nanosheets was detected byemploying X-ray photoelectron spectroscopy (XPS, Kratos Axis). Theinstrument was equipped with monochromated (Al Kα) X-ray guns.Calculation of the binding energy was carried out by calibrating thebinding energy of the C 1 s peak to 284.6 eV.

FIGS. 2-7 show the structural and compositional characterization ofCu—Au two-dimensional nanostructures prepared according to ExampleII(a).

From the scanning electron microscopy (SEM) image in FIG. 2, it is clearthat the hollow Au—Cu two-dimensional nanostructures have an averagediameter of 75 nm. Because the galvanic replacement reaction does notchange the size of Cu nanosheets, based on the size range of prepared Cunanosheets from 45 nm to a few micrometers, similar size range of Cu—Auhollow two-dimensional nanostructures can also be obtained. It wasdetermined that the galvanic replacement reaction is impacts theformation of the hollowness. Because the potential of Au³⁺/Au (1.40 V)is higher than that of Cu²⁺/Cu (0.34 V), this reaction,2Au³⁺+3Cu→2Au+3Cu², will spontaneously occur. The replacement of Cuatoms thus leads to the formation of the hollow nanostructures.

The transmission electron microscopy (TEM) image shown in FIG. 3 and thehigh-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM) measurements as shown in FIG. 5 further confirm Cu—Autwo-dimensional nanostructures with hollow pores.

The high-resolution TEM (HRTEM) image shown in FIG. 4 of an individualhollow nanostructure reveals that it contains large crystalline domains.The fringes with a lattice spacing of 2.225 Å can be indexed to the(111) plane of face centered cubic (fcc) alloy Cu—Au nanostructures.

FIG. 5 shows the energy dispersive X-ray (EDX) mapping image of thehollow nanostructure. FIGS. 6 and 7 show the EDX mapping image of Cuelement and the Au element, respectively. As shown in FIGS. 5-7, both Cuand Au are homogeneously distributed throughout the hollownanostructures. This indicates that the Cu—Au hollow nanostructures arein an alloying phase.

The transition of pure Cu fcc phase to alloy Cu—Au phase is furtherconfirmed by X-ray diffraction technology. FIG. 8 shows the Cu—Aualloying evolution process of Example II(a) over time. In particular,FIG. 8 shows the Cu—Au alloying evolution process with decreasingintensity of Cu (111) diffraction peak and increasing intensity of theCu—Au (111) diffraction peak.

Specifically, FIG. 8(a) shows that the pure Cu phase is obtained afterinjecting the Cu precursor at 300° C. for a reaction time of 60 minutes.The diffraction peak of Cu (111) is located at 43.7° as shown in FIG.8(a).

After injecting Au precursors into the Cu nanosheet solution for areaction time of 5 minutes at 120° C., FIG. 8(b) indicates the formationof the mixed phase because the diffraction peak of Cu—Au (111) appearsat 40.80. The porous structures further confirms the galvanicreplacement reaction occurring on the Cu sheet surface, as shown ininserted SEM image 81 and TEM image 82.

With the reaction time prolonged to 20 minutes, FIG. 8(c) indicates thediffraction peak of Cu (111) decreases to almost negligible, which meansthe product is now dominated by Cu—Au alloy phase. It was determinedthat under the same feeding concentration of Au precursors, theconcentration of Cu was shown to decrease with the reaction time. Themolar ratio of Cu to Au is about 3:1 when the reaction time is less than5 minutes. When the reaction time prolongs to 40 minutes, the molarratio of Cu to Au reduces to 1:3. The final molar ratio of Cu to Au willreach 1:8 after prolonging the reaction time to 60 minutes. Because thereaction rate of galvanic replacement increases with the concentrationof Au precursors, the molar ratio of Cu to Au and the time required toform hollow structures was found to decrease with increasedconcentrations of Au precursors. Thus, the composition and phase ofCu—Au two-dimensional nanostructures may be adjusted by controlling thereaction time and the injecting concentration of Au precursors.

The electronic properties and surface composition of Cu—Autwo-dimensional nanostructures was further examined by X-rayphotoelectron spectroscopy (XPS). FIGS. 9A and 9B show well resolvedpeaks from Au 4f and Cu 2p in the XPS spectra. Both peaks of Cu 2p arepositive shifted, i.e., 0.2 eV for Cu 2p_(1/2) and 0.3 eV for Cu2p_(5/2). The change of binding energy is likely due to the electrontransfer from Cu to Au and may also be explained by the work functiondifference of 4.65 eV for Cu (111) and 5.10 eV for Au (111).Furthermore, both peaks of Au 4f_(5/2) are also positive shifted, i.e.,0.2 eV for Au 4f_(7/2) and 0.13 eV for Au 4f_(5/2), respectively. Thischange is attributed to Au losing the electron to surface ligands. XPSanalysis indicates no isolated Au or Cu phase existed in thetwo-dimensional nanostructure, which is in agreement with XRD resultsand EDX mapping images.

The phase transition from pure Cu to Cu—Au alloy may also be visualizedwith the red-shift of their scattering spectrum. The absorption peak ofpure Cu nanosheets is located at around 600 nm. After forming the Cu—Autwo-dimensional hollow nanostructures, the extinction peak isred-shifted to infrared region (centered at 1500 nm), as shown in FIG.10. This red shift may be attributed to the decrease in aspect ratioduring galvanic replacement or the change of electronic structure due tophase transition. Cu—Au two-dimensional hollow nanostructures withunique optical property has potential applications in Surface EnhancedRaman Scattering (SERS), sensing, and biomedical fields.

FIGS. 11A and 11B show the SEM 111 and TEM 112 images of the Cu—Pd andCu—Pt, hollow nanostructures, respectively, prepared according toExamples II(b) and II(c). In particular, these SEM and TEM imagesindicate that hollow Cu—Pd and Cu—Pt two-dimensional nanostructures areformed due to the higher oxidation potential of Pd²⁺/Pd (0.92 V) andPt²⁺/Pt (1.20 V). The size of these two types of hollow nanostructuresmay be controlled from 50 nm to a few micrometers.

FIG. 11C shows SEM 111 and TEM 112 of Cu—Au nanotubes prepared accordingto Example II(d). In particular, the TEM image 111 indicates that theCu—Au nanotubes have rough surfaces and sharp tips, which may act ashigh efficiency catalysts for reducing CO₂ or for use as a gas sensor.

The invention claimed is:
 1. A method for preparing a hollowmulti-metallic nanostructure, the method comprising: providing a coppercomplex solution comprising one or more copper complexes, heating thecopper complex solution to provide a copper nanosheet solution, thecopper nanosheet solution comprising a copper nanosheet consistingessentially of a plurality of copper atoms, and providing a combinedsolution by combining the copper nanosheet solution with a metalprecursor solution comprising a metal precursor having second metalions, wherein the copper nanosheet solution is combined with the metalprecursor solution at temperature of between about 80 and 150 ° C. for areaction time of between about 20 and 120 minutes in order to perform asynthetic strategy, the synthetic strategy comprising: replacing aportion of the plurality of copper atoms with a corresponding number ofthe second metal ions, and promoting copper atom diffusion to providethe hollow multi-metallic nanostructure having a ratio of copper atomsto second metal atoms from about 10:1 to 1:10, wherein the combinedsolution has an initial molar ratio of copper atoms to second metal ionsof from about 5:1 to about 1:5.
 2. The method according to claim 1,wherein the copper atoms have a first oxidation potential, and whereinthe second metal ions are ions of a metal having a second oxidationpotential, the second oxidation potential being greater than the firstoxidation potential.
 3. The method according to claim 2, wherein thesecond oxidation potential is at least about 0.6 V greater than thefirst oxidation potential.
 4. The method according to claim 2, whereinthe second metal is selected from the group consisting of gold,platinum, palladium, and combinations thereof.
 5. The method accordingto claim 1, wherein the metal precursor is selected from the groupconsisting of chloroauric acid (HAuCl₄), palladium(II) acetylacetonate(Pd(acac)₂), chloroplatinic acid (H₂PtCl₆), combinations thereof, andhydrates thereof.
 6. The method according to 1, wherein the syntheticstrategy is a one-step synthetic strategy.
 7. The method according toclaim 1, wherein copper atom diffusion comprises copper atoms interiorto the copper nanosheet diffusing to an exterior of the coppernanosheet.
 8. A method for preparing a hollow multi-metal nanostructure,the method comprising: providing a copper nanosheet consistingessentially of copper atoms, wherein providing the copper nanosheetcomprises: providing a copper complex solution comprising one or morecopper complexes, heating the copper complex solution to provide acopper nanosheet solution, the copper nanosheet solution comprising thecopper nanosheet; providing a metal precursor solution comprising secondmetal ions, wherein the second metal is different from copper and has anoxidation potential of at least 0.6 V greater than an oxidationpotential of copper; and providing a combined solution by combining thecopper nanosheet solution and the metal precursor solution attemperature of between about 80 and 150° C. for a reaction time ofbetween about 20 and 120 minutes to replace one or more copper atoms ofthe copper nanosheet with the second metal ions and to form a hollowmulti-metal nanostructure comprising copper and the second metal,wherein the hollow multi-metal nanostructure has a ratio of copper atomsto second metal ions from about 10:1 to 1:10, and wherein the combinedsolution has an intial molar ratio of copper atoms to second metal ionsof from about 5:1 to about 1:5.